Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings

Segmueller T, Schlueter PA, Drees M, Schier A, Nogai S, Mitzel NW, Strassner T, Karsch HH (2007)
In: JOURNAL OF ORGANOMETALLIC CHEMISTRY. 692. ELSEVIER SCIENCE SA: 2789-2799.

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Abstract
At variance to an earlier finding, the reaction of Me2SiCl2 with Li[(Me)N-C(Ph)-NH] (1a), in the presence of a base, gives a six-membered ring molecule mu-[(Ph)(MeN)C-N][-SiMe2-N-C(Ph) N(Ph)-SiMe2-] (s3a), whereas with Li[(PrN)-Pr-i-C(Ph)-NH] (1b), a four-mernbered ring molecule mu-[(PrN)-Pr-i(Ph)C-N](2)(SiMe2)(2) (s4b) was formed. In contrast, with Li[(BuN)-Bu-t-C(Ph)-NH] (1c), no such reaction occurred. Obviously, a delicate influence of steric effects has to be taken into account. In fact, the latter amidinate reacts with GeCl2 to form an eight-membered ring molecule [(BuN)-Bu-t-C(Ph)-N-Ge](4) (5c) without adding an additional base. The compounds are fully characterized and their structures determined by X-ray diffraction. DFT calculations confirm the dependence on steric influences. The relative energies of ground and transition states give a rationalization the ease of transformations of the various rings via pathways with penta- and hexacoordinate silicon centers, which in turn relates to the experimental results on penta- and hexacoordinate silicon amidinates and their fluctional behavior in solution. (c) 2007 Elsevier B.V. All rights reserved.
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Segmueller T, Schlueter PA, Drees M, et al. Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings. In: JOURNAL OF ORGANOMETALLIC CHEMISTRY. Vol 692. ELSEVIER SCIENCE SA; 2007: 2789-2799.
Segmueller, T., Schlueter, P. A., Drees, M., Schier, A., Nogai, S., Mitzel, N. W., Strassner, T., et al. (2007). Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 692(13), 2789-2799.
Segmueller, T., Schlueter, P. A., Drees, M., Schier, A., Nogai, S., Mitzel, N. W., Strassner, T., and Karsch, H. H. (2007). “Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings” in JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 692, (ELSEVIER SCIENCE SA), 2789-2799.
Segmueller, T., et al., 2007. Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings. In JOURNAL OF ORGANOMETALLIC CHEMISTRY. no.692 ELSEVIER SCIENCE SA, pp. 2789-2799.
T. Segmueller, et al., “Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings”, JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 692, ELSEVIER SCIENCE SA, 2007, pp.2789-2799.
Segmueller, T., Schlueter, P.A., Drees, M., Schier, A., Nogai, S., Mitzel, N.W., Strassner, T., Karsch, H.H.: Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings. JOURNAL OF ORGANOMETALLIC CHEMISTRY. 692, p. 2789-2799. ELSEVIER SCIENCE SA (2007).
Segmueller, Thomas, Schlueter, Peter A., Drees, Markus, Schier, Annette, Nogai, Stefan, Mitzel, Norbert W., Strassner, Thomas, and Karsch, Hans H. “Dianionic amidinates at silicon and germanium centers: Four-, six- and eight-membered rings”. JOURNAL OF ORGANOMETALLIC CHEMISTRY. ELSEVIER SCIENCE SA, 2007.Vol. 692. 2789-2799.
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